Modified inorganic particles

ABSTRACT

The invention relates to modified inorganic particles with a layer structure with an average particle diameter of 5 nm to 20000 nm, comprising an outer shell consisting of aminoplasts which contain, interlamellarly, multifunctional C1-C30 amino compounds of the melamine, melamine derivative, urea, urea derivative, guanidine, guanidine derivative, cyanamide, dicyandiamide, sulphonamide and/or aniline-type. The invention also relates to the production of said modified inorganic particles and to their use in thermoplastics and duroplastics.

[0001] The invention relates to modified inorganic particles having alayer structure and a process for the preparation thereof and the usethereof.

[0002] Inorganic particles having a layer structure, such as clayminerals, and the modification thereof with dyes, polyhydric alcoholsand alkylammonium ions are known [Lagaly, G., Clay minerals (1981)16,1-21]. It is furthermore known that inorganic particles having a layerstructure can be used as plastics additives in elastomers (EP 0 484 245)and thermoplastics [Mülhaupt, R., Kunststoffe [Plastics] 87(1997)4,482-486]. A disadvantage is the high degree of agglomeration of thelayer-like clay minerals, so that it is not possible to distributelayer-like clay minerals in finely divided form in thermoplastic melts.

[0003] Known solutions for dispersing layer-like clay minerals havingparticle sizes of from 1 to 500 nm in plastics melts are the addition ofamine-substituted onium complexes (WO 93 04 117) or the dispersing ofphyllosilicates by dewatering and complexing with solutions ofwater-insoluble polymers (EP 0 822 163). However, these processes arevery complicated, and low molecular weight compounds in the blendsresult in a decrease in the strength of the blends.

[0004] An object of the present invention is to provide inorganicparticles having a layer structure which have good dispersibility inplastics and result in an improvement in the property spectrum ofthermoplastic and thermosetting plastics, in particular of polyolefins.

[0005] The object according to the invention was achieved by modifiedinorganic particles having a layer structure, modified inorganicparticles having a mean particle diameter of from 5 nm to 20 000 nm andan outer coat of from 0.1 to 20% by mass, based on the anhydrousinorganic particles, of aminoplasts and an interlamellar content of from20 to 5 000% by mass, based on the anhydrous inorganic particles, of amixture of from 50 to 98% by mass of substantially polyfunctional C₁-C₈₀amino compounds of the type consisting of melamine, melaminederivatives, urea, urea derivatives, guanidine, guanidine derivatives,cyanamide, dicyandiamide, sulfonamides and/or aniline and the saltsthereof and from 2 to 50% by mass of water.

[0006] Inorganic particles having a layer structure are, for example,silicates, phosphates, arsenates, titanates, vanadates, niobates,molybdates and/or manganates, in particular sheet silicates of the typeconsisting of montmorillonite, bentonite, kaolinite, muscovite,hectorite, fluorohectorite, canemite, revdite, grumantite, ilerite,saponite, beidelite, nontronite, stevensite, laponite, taneolite,vermiculite, halloysite, volkonskoite, magadite, rectorite, halloysite,kenyaite, sauconite, borofluorophlogopites and/or synthetic sheetsilicates, the sheet silicates furthermore particularly preferably beingsheet silicates having exchangeable cations of the type consisting ofalkali metal, alkaline earth metal, aluminum, iron and/or manganesecations.

[0007] Examples of suitable phosphates having a layer structure arecompounds of the formula H₂[M^(IV)(PO₄)₂]._(x)H₂O (M^(IV)=Zr, Ti, Ge,SN, Pb) and CaPO₄R.H₂O (R=CH₃; C₂H₅).

[0008] Examples of suitable arsenates having a layer structure arecompounds of the formula H₂[M^(IV)(AsO₄)₂]._(x)H₂O andH[Mn(AsO₄)₂]._(x)H₂O. Examples of suitable titanates having a layerstructure are compounds of the formula Na₄Ti₈O₂₀._(x)H₂O andK₂Ln₂Ti₃O_(10x)H₂O.

[0009] Synthetic sheet silicates are obtained, for example, by reactingnatural sheet silicates with sodium hexafluorosilicate.

[0010] Particularly preferred sheet silicates are those whose layershave an interlayer spacing of about 0.4 nm to 1.5 nm.

[0011] The aminoplasts of the outer coat of the modified inorganicparticles according to the invention and having a layer structure arepreferably melamine resins, urea resins, cyanamide resins, dicyandiamideresins, sulfonamide resins, guanamine resins and/or aniline resins.

[0012] Preferred melamine resins are polycondensates of melamine ormelamine derivatives and C₁-C₁₀-aldehydes having a molar melamine ormelamine derivative to C₁-C₁₀-aldehydes ratio of from 1:1 to 1:6 and thepartial etherification products thereof with C₁-C₁₀-alcohols, preferredmelamine derivatives being melamines, diaminomethyltriazines and/ordiaminophenyltriazines substituted by hydroxy-C₁-C₁₀-alkyl groups,hydroxy-C₁-C₄-alkyl(oxa-C₂-C₄-alkyl)₁₋₅ groups and/or byamino-C₁-C₁₂-alkyl groups, particularly preferably2-(2-hydroxyethylamino)-4,6-diamino-1,3,5-triazine,2-(5-hydroxy-3-oxapentylamino)-4,6-diamino-1,3,5-triazine and/or2,4,6-tris(6-aminohexylamino)-1,3,5-triazine, ammeline, ammelide, melem,melon, melam, benzoguanamine, acetoguanamine,tetramethoxymethylbenzoguanamine, caprinoguanamine and/orbutyroguanamine, and the C₁-C₁₀-aldehyde are preferably formaldehyde,acetaldehyde, trimethylolacetaldehyde, acrolein, furfurol, glyoxaland/or glutaraldehyde, particularly preferably formaldehyde.

[0013] The melamine resins in the outer coat of the modified inorganicparticles according to the invention and having a layer structure canlikewise contain from 0.1 to 10% by mass, based on the sum of melamineand melamine derivatives, of incorporated phenols and/or urea. Suitablephenol components here are phenol, C₁-C₉-alkylphenol, hydroxyphenolsand/or bisphenols.

[0014] Examples of partial etherification products of melamine resinswith C₁-C₁₀-alcohols are methylated or butylated melamine resins.

[0015] Examples of urea resins optionally contained as aminoplasts inthe outer coat of the modified inorganic particles according to theinvention and having a layer structure are also cocondensates withphenols, acid amides or sulfonamides, in addition to urea/formaldehyderesins.

[0016] Examples of sulfonamide resins optionally contained asaminoplasts in the outer coat of the modified inorganic particlesaccording to the invention and having a layer structure are sulfonamideresins obtained from p-toluenesulfonamide and formaldehyde.

[0017] Examples of guanamine resins optionally contained as aminoplastsin the outer coat of the modified inorganic particles according to theinvention and having a layer structure are resins which containbenzoguanamine, acetoguanamine, tetramethoxymethylbenzoguanamine,caprinoguanamine and/or butyroguanamine as guanamine components.

[0018] Examples of aniline resins optionally contained as aminoplasts inthe outer coat of the modified inorganic particles according to theinvention and having a layer structure are aniline resins which, inaddition to aniline, may also contain toluidine and/or xylidines asaromatic diamines.

[0019] The melamine derivatives optionally forming an interlamellarcontent in the modified inorganic particles according to the inventionand having a layer structure are preferably melamines,diaminomethyltriazines and/or diaminophenyltriazines substituted byhydroxy-C₁-C₁₀-alkyl groups, hydroxy-C₁-C₁₀-alkyl(oxa-C₂-C₄-alkyl)₁₋₅groups and/or by amino-C₁-C₁₂-alkyl groups, preferably2-(2-hydroxyethylamino)-4,6-diamino-1,3,5-triazine,2-(5-hydroxy-3-oxapentylamino)-4,6-diamino-1,3,5-triazine,2,4,6-tris(6-aminohexylamino)-1,3,5-triazine and/or2,4-(di-5-hydroxy-3-oxapentylamino)-6-methyl-1,3,5-triazine, ammeline,ammelide, melem, melon and/or melam.

[0020] The urea derivatives optionally forming an interlamellar contentin the modified inorganic particles according to the invention andhaving a layer structure are thiourea and urea or thiourea substitutedby C₁-C₁₀-alkyl groups, C₆-C₁₄-aryl groups, hydroxy-C₁-C₁₀-alkyl groups,hydroxy-C₁-C₄-alkyl(oxa-C₂-C₄-alkyl)₁₋₅ groups and/or byamino-C₁-C₁₂-alkyl groups.

[0021] The salts of melamine, melamine derivatives, urea, ureaderivatives, guanidine, guanidine derivatives, cyanamide, dicyandiamide,sulfonamides and/or aniline which optionally form an interlamellarcontent in the modified inorganic particles according to the inventionand having a layer structure are preferably salts having inorganicand/or organic anions, in particular fluorides, chlorides, bromides,iodides, sulfates, phosphates, borates, silicates, cyanurates,tosylates, formates, acetates, propionates, butyrates and/or maleates.

[0022] The modified inorganic particles having a layer structure areprepared, according to the invention, by a process in which suspensionsof inorganic particles having a layer structure in water or mixtures offrom 5 to 99% by weight of water and from 95 to 1% by mass ofC₁-C₈-alcohols, having a solids content of from 2 to 35% by mass, arehomogenized, in a stirred reactor at 20 to 100° C. and in a residencetime of from 10 to 180 min, with solutions or suspensions ofpolyfunctional C₁-C₃₀ amino compounds of the type consisting ofmelamine, melamine derivatives, urea, urea derivatives, guanidine,guanidine derivatives, cyanamide, dicyandiamide, sulfonamides and/oraniline and the salts thereof in water or mixtures of from 5 to 99% byweight of water and from 95 to 1% by mass of C₁-C₈alcohols, having asolids content of from 5 to 90% by mass, the amount by mass of thepolyfunctional C₁-C₃₀ amino compounds being from 20 to 5 000% by mass,based on the anhydrous inorganic particles, following the dispersion ofthe laden inorganic particles, optionally after the liquid phase hasbeen partially separated off, aminoplast prepolymers of the typeconsisting of melamine resins, urea resins, cyanamide resins,dicyandiamide resins, sulfonamide resins, guanamine resins and/oraniline resins having a number average molar mass of from 150 to 1 000being introduced as a solution in water and/or in organic solvents orsolvent mixtures, having a resin content of from 30 to 98% by mass, andoptionally from 0.1 to 2.0% by mass, based on the aminoplastprepolymers, of acidic catalysts are introduced at from 20 to 90° C. andare reacted, the aminoplast content of the dispersion being from 0.1 to20% by mass, based on the anhydrous inorganic particles, the solidscontent comprising inorganic particles in the dispersion being from 0.5to 35% by mass and the residence time being from 10 to 45 min, andthereafter the modified inorganic particles are dried at from 20 to 180°C. and in a residence time of from 0.1 to 8 hours with removal of theliquid phase.

[0023] A further process for the preparation of the modified inorganicparticles having a layer structure comprises, according to theinvention, homogenizing suspensions of inorganic particles having alayer structure in water or mixtures of from 5 to 99% by weight of waterand from 95 to 1% by mass of C₁-C₈-alcohols, having a solids content offrom 2 to 35% by mass, in a stirred reactor at from 20 to 100° C. and ina residence time of from 10 to 180 min, with solutions or suspensions ofpolyfunctional C₁-C₃₀ amino compounds of the type consisting ofmelamine, melamine derivatives, urea, urea derivatives, cyanamide,dicyandiamide, sulfonamides guanidine, guanidine derivatives and/oraniline and the salts thereof in water or mixtures of from 5 to 99% byweight of water and from 95 to 1% by mass of C₁-C₈-alcohols, having asolids content of from 5 to 90% by mass, the amount by mass of thepolyfunctional C₁-C₃₀ amino compounds being from 20 to 5 000% by mass,based on the anhydrous inorganic particles, following the dispersion ofthe laden inorganic particles, optionally after the liquid phase hasbeen partially separated off, adding from 0.1 to 10% by mass, based onthe anhydrous inorganic particles, of C₁-C₁₀-aldehydes as from 5 to 50%solutions in water or mixtures of from 5 to 99% by weight of water andfrom 95 to 1% by mass of C₁-C₈-alcohols, which optionally contain from0.05 to 1.0% by mass, based on the C₁-C₁₀-aldehydes, of acidiccatalysts, in the course of from 10 to 90 min at from 50 to 90° C., andthereafter drying the modified inorganic particles at from 20 to 180° C.and in a residence time of from 0.1 to 8 hours with removal of theliquid phase.

[0024] The C₁-C₁₀-aldehydes used in the preparation of the modifiedinorganic particles are preferably formaldehyde, acetaldehyde,trimethylolacetaldehyde, acrolein, benzaldehyde, furfurol, glyoxal,glutaraldehyde, phthalaldehyde and/or terephthalaldehyde, particularlypreferably formaldehyde.

[0025] Examples of suitable acidic catalysts in the process according tothe invention for the preparation of modified inorganic particles havinga layer structure are inorganic acids, such as hydrochloric acid orsulfuric acid, and/or organic acids, such as formic acid, acetic acid,oxalic acid, p-toluenesulfonic acid or lactic acid. Acids having abuffer function, such as citric acid, acetic acid and/or phosphoricacid, or acidic salts having a buffer function, such as sodium hydrogenphosphate or potassium hydrogen phosphate, are preferred.

[0026] The modified inorganic particles are suitable in particular forflameproofing plastics, preferably in combination with inorganic and/ororganic salts having ammonium, alkylammonium, arylammonium, phosphonium,alkylphosphonium, arylphosphonium, alkali metal and/or alkaline earthmetal cations and/or phosphate, phosphite, phosphonate, silicate and/orborate anions and/or with polyhydric alcohols of the type consisting oferythritol, pentaerythritol, pentitol and/or hexitol, and as additivesfor increasing the scratch resistance and UV stability and for improvingthe barrier properties of plastics and plastics laminates, and as acatalyst or catalyst support.

[0027] When the modified inorganic particles are used as a plasticsadditive, it is advantageous to add from 0.1 to 5% by mass, based on themodified inorganic particles, of water-soluble, water-dispersible and/orwater-emulsifiable polymers, preferably polyvinyl alcohol, polyvinylacetate, maleic anhydride copolymers and/or saturated or unsaturatedpolyesters, to the modified inorganic particles.

[0028] When a modified inorganic particle is used as an additive forflameproofing plastics, particularly preferred combinations are thosewhich contain ammonium polyphosphate and pentaerythritol.

[0029] Further polyolefins according to the invention are those having acontent of from 1 to 60% by mass, based on the polyolefins used, ofmodified inorganic particles having a layer structure and optionally, asfurther additives, inorganic or organic salts, fillers, reinforcingmaterials, polymeric dispersants, assistants and/or polyhydric alcohols,

[0030] it being possible for the inorganic or organic salts to be saltshaving ammonium, alkylammonium, phosphonium, alkylphosphonium,arylphosphonium, alkali metal and/or alkaline earth metal cations and/orsalts having phosphite, phosphate, phosphonate, silicate and/or borateanions, which may be contained in an amount of up to 25% by mass in thepolyolefin,

[0031] the fillers and/or reinforcing materials being inorganic ororganic fillers and/or fibers, which may be contained in an amount of upto 40% by mass in the polyolefin,

[0032] the polymeric dispersants being water-soluble, water-dispersibleand/or water-emulsifiable polymers which may be contained in an amountof up to 3% by mass in the polyolefin,

[0033] and the polyhydric alcohols being polyhydric alcohols of the typeconsisting of erythritol, pentaerythritol, pentitol and/or hexitol,which may be contained in an amount of up to 15% by mass in thepolyolefin.

[0034] The amount of the modified inorganic particles having a layerstructure is preferably from 3 to 30% by mass, based on the polyolefins.

[0035] The polyolefins according to the invention, containing modifiedinorganic particles having a layer structure and optionally furtheradditives, have an improved property spectrum with respect to a degreeof flameproofing, toughness, scratch resistance, UV stability andbarrier properties.

[0036] The polyolefins according to the invention, containing modifiedinorganic particles having a layer structure and optionally furtheradditives, are preferably poly-C₂-C₅-α-olefins or copolymers ofC₂-C₅-α-olefins and α-olefins having 2 to 18 C atoms of the typeconsisting of linear and/or branched polyethylene homo- and/orcopolymers, cycloolefin/ethylene copolymers, polypropylene homopolymers,random propylene copolymers, propylene block copolymers, randompropylene block copolymers, isotactic poly-but-1-ene and/or4-methylpent-1-ene homo- and/or copolymers.

[0037] Al₂O₃, Al(OH)₃, barium sulfate, calcium carbonate, glass beads,silica, mica, quartz powder, slate powder, hollow microspheres, carbonblack, talc, crushed rock, woodmeal and/or cellulose powder may bepresent as fillers in the polyolefins according to the invention,containing modified inorganic particles having a layer structure andoptionally further additives.

[0038] Examples of reinforcing materials in the polyolefins according tothe invention, containing modified inorganic particles having a layerstructure and optionally further additives, are wood fibers, cellulosefibers, flax, jute and kenaf.

[0039] Preferred reinforcing materials which may be contained in thepolyolefins according to the invention, containing modified inorganicparticles having a layer structure and optionally further additives, areinorganic fibers, in particular glass fibers and/or carbon fibers,natural fibers, in particular cellulose fibers, and/or plastic fibers,in particular fibers of polyacrylonitrile, polyvinyl alcohol, polyvinylacetate, polypropylene, polyesters and/or polyamides.

[0040] Water-soluble, water-dispersible and/or water-emulsifiablepolymers may be present as polymeric dispersants in the polyolefinsaccording to the invention, containing modified inorganic particleshaving a layer structure and optionally further additives.

[0041] Examples of water-soluble polymers which may be contained in thepolyolefins according to the invention, containing modified inorganicparticles having a layer structure and optionally further additives, arepolyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, polyethyleneoxide, methylcellulose, ethylcellulose, hydroxyethylcellulose and/orcarboxymethylcellulose.

[0042] The water-dispersible or water-emulsifiable polymers optionallycontained in the polyolefins according to the invention, containingmodified inorganic particles having a layer structure and optionallyfurther additives, are thermoplastics, elastomers and/or waxes.

[0043] Examples of suitable thermoplastics are cellulose esters,cellulose ethers, polyvinyl acetate, polyvinyl propionate,polyacrylates, unsaturated or saturated polyesters, maleic anhydridecopolymers, polypropylene oxide and/or ethylene/vinyl acetatecopolymers. Preferred maleic anhydride copolymers are copolymers inwhich the anhydride groups have been modified by amidation and/orimidation with hydrophobic hydrocarbon substituents or esterificationwith hydrophilic polyalkylene oxide substituents.

[0044] Examples of water-dispersible or water-emulsifiable elastomersare styrene/butadiene rubbers, acrylate rubbers, polyurethanes and/orfluoroelastomers.

[0045] Examples of suitable waxes are polyolefin wax oxidates, such aspolyethylene wax oxidates, or waxes based on ethylene/vinyl acetatecopolymers.

[0046] Particularly preferred polymeric dispersants which are optionallycontained in the polyolefins according to the invention, containingmodified inorganic particles having a layer structure and optionallyfurther additives, are polyvinyl alcohol, polyvinyl acetate, maleicanhydride copolymers and/or unsaturated or saturated polyesters.

[0047] The polyolefins according to the invention, containing modifiedinorganic particles having a layer structure and optionally furtheradditives, can be prepared by a process in which mixtures ofpolyolefins, modified inorganic particles and optionally, as furtheradditives, inorganic or organic salts, fillers, reinforcing materials,polymeric dispersants in the form of solutions, dispersions oremulsions, assistants and/or polyhydric alcohols are melted incontinuous kneaders, or in which polyolefins are melted in continuouskneaders and the modified inorganic particles and optionally inorganicor organic salts, fillers, reinforcing materials, polymeric dispersantsin the form of solutions, dispersions or emulsions and/or polyhydricalcohols are metered into the polymer melt, the mixtures are homogenizedat melt temperatures of from 30 to 100 degrees above the melting pointor softening point of the polyolefins, optionally degassed in vacuo,discharged and granulated, or molded directly from the melt to givesemifinished products or moldings, the content of modified inorganicparticles having a layer structure and optionally, as further additives,inorganic or organic salts, fillers, reinforcing materials, polymericdispersants, assistants and/or polyhydric alcohols in the polyolefinsbeing from 1 to 60% by mass, based on the polyolefins used.

[0048] Continuous kneaders used in the preparation of the polyolefinsaccording to the invention, containing modified inorganic particleshaving a layer structure and optionally further additives, arepreferably twin-screw extruders having an L/D of from 30 to 48 orsingle-screw extruders having a plunger screw.

[0049] In the preparation, from 0.01 to 2.5% by mass of stabilizers,from 0.1 to 1% by mass of antistatic agents and/or from 0.01 to 5% bymass of processing assistants, based in each case on the polyolefinsused, can furthermore be added as assistants.

[0050] Suitable stabilizers are preferably mixtures of from 0.01 to 0.6%by mass of phenolic antioxidants, from 0.01 to 0.6% by mass of3-arylbenzofuranones, from 0.01 to 0.6% by mass of processingstabilizers based on phosphites, from 0.01 to 0.6% by mass of hightemperature stabilizers based on disulfides and thioethers and/or from0.01 to 0.8% by mass of sterically hindered amines (HALS).

[0051] Processing assistants which may be added in the preparation ofthe polyolefins according to the invention, containing modifiedinorganic particles having a layer structure and optionally furtheradditives, are calcium stearate, magnesium stearate and/or waxes.

[0052] The polyolefins or olefin copolymers used in the preparation ofthe polyolefins according to the invention, containing modifiedinorganic particles having a layer structure and optionally furtheradditives, preferably contain from 0.05 to 2% by mass, based on thepolyolefins used, of olefin copolymers and/or olefin graft copolymerscontaining acid, acid anhydride and/or epoxide groups, preferablyethylene/butyl acrylate/acrylic acid terpolymers having an acrylic acidcontent of from 0.1 to 2% by mass or maleic anhydride-graftedpolypropylene having a maleic anhydride content of from 0.05 to 0.5% bymass, as a compatibilizer for the modified inorganic particles having alayer structure and the inorganic or organic salts and/or polyhydricalcohols. The olefin graft copolymers can be prepared by customaryprocesses, by reacting the polyolefin with the unsaturated monomer inthe presence of thermal free radical initiators in the solid phase or inthe melt.

[0053] The polyolefins according to the invention, containing modifiedinorganic particles having a layer structure and optionally furtheradditives, have an improved property spectrum, in particular a gooddegree of flameproofing. They are used in particular as films, fibers,sheets, pipes, coatings, hollow bodies, injection molded products andfoams. The particular advantage of these semifinished products andmoldings is the improved degree of flameproofing, toughness, scratchresistance and UV stability and the improved barrier properties.

[0054] Thermosetting plastics containing from 2 to 80% by mass, based onthe thermosetting plastics used, of modified inorganic particles havinga layer structure and optionally, as further additives, inorganic ororganic salts, fillers, reinforcing materials, polymeric dispersants,assistants and/or polyhydric alcohols are furthermore according to theinvention,

[0055] the inorganic or organic salts being salts having ammonium,alkylammonium, phosphonium, alkylphosphonium, arylphosphonium, alkalimetal and/or alkaline earth metal cations and/or salts having phosphite,phosphate, phosphonate, silicate and/or borate anions, which may becontained in an amount of up to 60% by mass in the thermosettingplastics,

[0056] the fillers and/or reinforcing materials being inorganic ororganic fillers and/or fibers, which may be contained in an amount of upto 70% by mass in the thermosetting plastics,

[0057] the polymeric dispersants being water-soluble, water-dispersibleand/or water-emulsifiable polymers which may be contained in an amountof up to 5% by mass in the thermosetting plastics,

[0058] and the polyhydric alcohols being polyhydric alcohols of the typeconsisting of erythritol, pentaerythritol, pentitol and/or hexitol,which are contained in an amount of up to 30% by mass in thethermosetting plastics.

[0059] The thermosetting plastics preferably contain from 5 to 50% bymass of modified inorganic particles, based on the thermosettingplastics.

[0060] Examples of thermosetting plastics are melamine resins, urearesins, guanamine resins, cyanamide resins, dicyandiamide resins,sulfonamide resins or aniline resins.

[0061] The thermosetting plastics may consist of aminoplasts of the samecomposition which may be a component of the outer coat of the modifiedinorganic particles.

[0062] The further additives optionally contained in the thermosettingplastics containing modified inorganic particles having a layerstructure may be additives which may also be contained in thepolyolefins containing modified inorganic particles having a layerstructure and optionally further additives.

[0063] The thermosetting plastics according to the invention, containingmodified inorganic particles having a layer structure and optionallyfurther additives, are prepared by a process in which mixtures ofprecondensates of thermosetting plastics, modified inorganic particleshaving a layer structure and optionally, as further additives, inorganicor organic salts, fillers, reinforcing materials, polymeric dispersantsin the form of solutions, dispersions or emulsions, assistants and/orpolyhydric alcohols are molded by customary processes to givesemifinished products or moldings and are cured, the content of modifiedinorganic particles having a layer structure and optionally, as furtheradditives, inorganic or organic salts, fillers, reinforcing materials,polymeric dispersants, assistants and/or polyhydric alcohols in theblends being from 1 to 80% by mass, based on the thermosetting plasticsused,

[0064] the inorganic or organic salts being salts having ammonium,alkylammonium, phosphonium, alkylphosphonium, arylphosphonium, alkalimetal and/or alkaline earth metal cations and/or salts having phosphite,phosphate, polyphosphates, phosphonates, silicate and/or borate anions,which may be contained in an amount of up to 45% by mass in thethermosetting plastic,

[0065] the fillers and/or reinforcing material being inorganic ororganic fillers and/or fibers which may be contained in an amount of upto 60% by mass in the thermosetting plastic,

[0066] the polymeric dispersants being water-soluble, water-dispersibleand/or water-emulsifiable polymers which may be contained in an amountof up to 5% by mass in the thermosetting plastic,

[0067] and the polyhydric alcohols being polyhydric alcohols of the typeconsisting of erythritol, pentaerythritol, pentitol and/or hexitol,which may be contained in an amount of up to 15% by mass in thethermosetting plastic.

[0068] A preferred variant for the preparation of thermosetting plasticsaccording to the invention, containing modified inorganic particleshaving a layer structure and optionally further additives, comprisespreparing the precondensates of the thermosetting plastics bypolycondensation of the monomers on which the precondensates of thethermosetting plastics are based, in the presence of the modifiedinorganic particles having a layer structure and optionally, as furtheradditives, inorganic or organic salts, fillers, reinforcing materials,assistants polymeric dispersants and/or polyhydric alcohols.

[0069] The water-soluble, water-dispersible and/or water-emulsifiablepolymers optionally contained, as polymeric dispersants, in thethermosetting plastics according to the invention, containing modifiedinorganic particles having a layer structure and optionally furtheradditives, can likewise be formed in situ in the preparation of thethermosetting plastics, by adding to the mixtures present as aqueousdispersions or emulsions and comprising precondensates of aminoplastsand modified inorganic particles having a layer structure, before thepreparation of the thermosetting plastics, instead of polymericdispersants, mixtures of ethylenically unsaturated monomers and thermalfree radical initiators, from which the water-soluble, water-dispersibleand/or water-emulsifiable polymers are formed. Examples of suitableethylenically unsaturated monomers are acrylamide, vinylpyrrolidone,C₄-C₁₈-(meth)acrylic esters and/or vinyl acetate.

[0070] Preferred semifinished products and moldings of polyolefins orthermosetting plastics containing modified inorganic particles having alayer structure and optionally further additives are films, prepregs,fibers, sheets, pipes, coatings, hollow bodies, injection moldedproducts and foams.

[0071] The semifinished products and moldings according to theinvention, comprising polyolefins containing modified inorganicparticles having a layer structure and optionally further additives, canbe prepared by customary methods for processing thermoplastics,poly-C₂-C₅-α-olefins or copolymers of C₂-C₅-α-olefins and α-olefinshaving 2 to 18 C atoms, containing modified inorganic particles having alayer structure and optionally, as further additives, inorganic ororganic salts, fillers, reinforcing materials, polymeric dispersants,assistants and/or polyhydric alcohols being melted in continuouskneaders, preferably in extruders having an L/D of from 30 to 48, attemperatures of from 30 to 120° C. above the melting points or softeningpoints of the polyolefins, homogenized, and

[0072] A) discharged via an annular die, taken off as a blown film byforcing in air and rolled up, or

[0073] B) discharged via a slot die, applied to a chill roll unit andtaken off as cover film and rolled up or, in the case of chill rollunits having a plurality of slot dies, taken off as coextrusion film androlled up, or

[0074] C) added as a melt to a roll mill and then to a calender andtaken off as thermoformed film and rolled up or sealed on continuoussheets of metal foils, plastics films, paper webs or textile webs andtaken off as multicomponent laminates and rolled up, or

[0075] D) added as a melt to a calender and taken off as thermoformedfilm and rolled up, taken off as a sheet via conveyor belts and cut orsealed on continuous sheets of metal foils, plastics films, paper websor textile webs and taken off as multicomponent laminates and rolled up,or

[0076] E) discharged via a profiled die and taken off as a profile, cutand fabricated, or

[0077] F) discharged via an annular die, taken off as a tube by forcingin air and rolled up or taken off as a pipe, cut and fabricated, or

[0078] G) discharged via a slot die after metering in blowing agents ordischarged via an annular die by forcing in air and taken off as a foamsheet and rolled up or discharged via a circular die, taken off as anextrudate and cut into particle foam segments, or

[0079] H) discharged via a slot die of a pipe coating unit and sealed inmolten form on the rotating pipe, or

[0080] I) discharged via an annular die with prior introduction of theconductors or of the made-up single cable and taken off as single cableor as made-up single cables provided with a cable sheath and rolled up,or

[0081] K) extruded through annular dies as a parison, shaped by blowingout in a heated divided blow mold for hollow bodies and optionally beingsubjected, in a second blow mold, to additional longitudinal stretchingby means of a stretching plunger, a further radial stretching by meansof blown air, or

[0082] L) injected into a heated injection mold for the production ofthe parison and, after removal, optionally preferably separate heatingof the parison in a conditioning mold, transferred to the blow mold andshaped by blowing out to give a hollow body, or

[0083] M) processed in injection molding machines, preferably withthree-zone screws having a screw length of from 18 to 24 D, and highinjection speeds and at mold temperatures of from 5 to 70° C., to giveinjection molded articles, or

[0084] N) melted in melt spinning units comprising plastifying extruder,melt pump, melt distributor, capillary mold, blow shaft and downstreamapparatuses and extruded by means of the melt pump through the capillarymold into the blow shaft and taken off as filaments and furtherprocessed in downstream apparatuses.

[0085] Suitable processes for the production of semifinished productsand moldings from mixtures of precondensates of thermosetting plastics,modified inorganic particles having a layer structure and optionallyfurther additives to give semifinished products and moldings are

[0086] formulations to give molding materials and thermoprocessing togive compression moldings, injection moldings, filaments or profiles bycompression molding, injection molding, melt spinning or extrusion, or

[0087] processing of solutions of the precondensates of thermosettingplastics, which precondensates contain the modified inorganic particleshaving a layer structure in dispersed form, to give thermosettingplastics fibers by centrifugal spinning, filament drawing, extrusion orfibrillation processes, optionally subsequent orientation, and curing,or

[0088] processing of solutions of the precondensates of thermosettingplastics, which precondensates contain the modified inorganic particleshaving a layer structure in dispersed form, to give microcapsules byintroduction into an emulsifier-free aqueous dispersion of solid orliquid capsule core formers, curing and spray-drying, or

[0089] processing of solutions of the precondensates of thermosettingplastics, which precondensates contain the modified inorganic particleshaving a layer structure in dispersed form, to give closed-cell foams byintroduction into an emulsifier-free aqueous dispersion of volatilehydrocarbons, inert gases and/or inorganic carbonates, and discharge ofhollow particles either into molds and curing to give closed-cell foamsor through a mold and curing to give closed-cell foamed profiles, or

[0090] processing of solutions of the precondensates of thermosettingplastics, which precondensates contain the modified inorganic particleshaving a layer structure in dispersed form, to give open-cell foams byintroduction into an aqueous blowing agent emulsion of volatilehydrocarbons, inert gases and/or inorganic carbonates, heating to theboiling point or decomposition point of the blowing agent and dischargeeither into molds and curing to give open-cell foams or through a moldand curing to give open-cell foamed profiles, or

[0091] production of coatings by formulation of solutions of theprecondensates of the thermosetting plastics, which precondensatescontain the modified inorganic particles having a layer structure indispersed form, to give coating resin solutions or coating resindispersions and subsequent discharge of coating resin solutions orcoating resin dispersions onto sheet-like substrate materials, dryingand curing, or

[0092] production of laminates by formulation of solutions of theprecondensates of thermosetting plastics, which precondensates containthe modified inorganic particles having a layer structure in dispersedform, to give impregnating resin solutions or impregnating resindispersions and subsequent impregnation of sheet-like substratematerials, lamination and curing, or

[0093] processing of precondensates of thermosetting plastics, whichprecondensates contain the modified inorganic particles having a layerstructure in dispersed form, by the casting resin technology to givesemifinished products, moldings or coatings.

EXAMPLE 1

[0094] In a 20 l stirred reactor having a bottom drain valve, a mixtureof 600 g of melamine, 600 g of sodium montmorillonite (Südchemie AG,Moosburg, Federal Republic of Germany) and 12 l of water is heated to80° C. and stirred for 2 hours, the sodium montmorillonite swelling. ThepH of the suspension is adjusted to pH=5.0 with 115 g of HCl and, afterstirring for 1 hour at 80° C., 360 ml of formaldehyde (30%) are added inthe course of 30 min. After stirring for 2 hours at 80° C., the modifiedinorganic particles are separated off in a cellular filter, washedchloride-free and dried in vacuo at 75° C./8 hours. The yield ofmodified sodium montmorillonite is 1200 g.

[0095] The primary particles of the modified sodium montmorillonite havea mean particle diameter of 150 nm, determined by transmission electronmicroscopy.

[0096] ATR investigations of the modified inorganic particle indicated asurface coating of the particles with melamine/formaldehyde resin.

[0097] For determining the content of free intercalated melamine in theintermediate silicate layers, 12 g of the modified inorganic particleshaving a layer structure were extracted for 48 hours with water. Afterconcentration of the extract and vacuum drying, 5.2 g of a white powderwere obtained. The dissolution in water and fractionation by means ofHPLC (Waters HPLC 2690, UV detection at 220 nm, Develosil RP aquaeuscolumn 5 mcm 250×2 mm, elution by 0.05 M NaH₂PO₄/acetonitrile (solventgradient) gave the following composition, based on the amount ofmelamine starting material: 68% by mass of melamine and 32% by mass ofhydroxymethylolmelamine and higher molecular weight oligomers.

EXAMPLE 2

[0098] In a 20 l stirred reactor having a bottom drain valve, a mixtureof 500 g of melamine, 50 g of urea, 50 g of thiourea, 600 g of calciummontmorillonite (Südchemie AG, Moosburg, Federal Republic of Germany)and 12 l of water is heated to 80° C. and stirred for 2 hours, thecalcium montmorillonite swelling. The pH of the suspension is adjustedto about pH=5.0 with 115 g of HCl and, after stirring for 1 hour at 80°C., 450 ml of a mixture of formaldehyde (30%) and glutaraldehyde (50%),molar ratio 4:1, are [lacuna] in the course of 30 min. After stirringfor 2 hours at 80° C., the modified inorganic particles are separatedoff in a cellular filter, washed chloride-free and dried in vacuo at 75°C./8 hours. The yield of modified calcium montmorillonite is 1 150 g.

[0099] The primary particles of the modified calcium montmorillonitehave a mean particle diameter of 650 nm, determined by transmissionelectron microscopy.

[0100] ATR investigations of the modified inorganic particle indicated asurface coating of the particles with aminoplast.

[0101] For determining the content of free intercalated polyfunctionalamino compounds in the intermediate silicate layers, 12 g of themodified inorganic particles having a layer structure were extracted for48 hours with water. After concentration of the extract and vacuumdrying, 5.0 g of a white powder were obtained. The dissolution in waterand fractionation by means of HPLC (Waters HPLC 2690, UV detection at220 nm, Develosil RP aquaeus column 5 mcm 250×2 mm, elution by 0.05 MNaH₂PO₄/acetonitrile (solvent gradient) gave the following composition,based on the amount of starting materials in the form of polyfunctionalamino compounds: 60% by mass of melamine, 6% by mass of urea, 6% by massof thiourea, 28% by mass of methylolated polyfunctional amino compoundsand higher molecular weight oligomers.

EXAMPLE 3

[0102] 5 kg of 30% aqueous formalin solution and 1.74 kg of melamine areintroduced into a 10 l stirred reactor and condensed at 80° C. withstirring in the course of 120 min.

[0103] In a second 200 l stirred reactor having a turbo stirrer, amixture of 6 kg of melamine, 6 kg of sodium montmorillonite (SüdchemieAG, Moosburg, Federal Republic of Germany) and 120 of water is heated to80° C. and stirred for 2 hours, the sodium montmorillonite swelling. ThepH of the suspension is adjusted to pH=5.0 with 1.15 kg of HCl andstirring is effected for 1 hour at 80° C. After cooling to roomtemperature, an aqueous solution of the aminoplast precondensate isadded to the stirred dispersion in the course of 30 min at high mixingintensity (40 m/s). After a reaction time of 60 min, the dispersion isdischarged and the modified inorganic particles are separated off in acellular filter, washed chloride-free and dried in vacuo at 75° C./8hours. The yield of modified sodium montmorillonite is 13.4 kg.

[0104] The primary particles of modified sodium montmorillonite have amean particle diameter of 950 nm, determined by transmission electronmicroscopy.

[0105] ATR investigations of the modified inorganic particles indicateda surface coating of the particles with melamine resin.

[0106] For determining the content of free intercalated melamine in theintermediate silicate layers, 12 g of the modified inorganic particleshaving a layer structure were extracted for 48 hours with water. Afterconcentration of the extract and vacuum drying, 5.6 g of a white powderwere obtained. The dissolution in water and fractionation by means ofHPLC (Waters HPLC 2690, UV detection at 220 nm, Develosil RP aquaeuscolumn 5 mcm 250×2 mm, elution by 0.05 M NaH₂PO₄/acetonitrile (solventgradient) gave the following composition, based on the amount ofmelamine starting material: 71% by mass of melamine and 29% by mass ofhydroxymethylolmelamine and higher molecular weight oligomers.

EXAMPLE 4

[0107] 5.4 kg of 30% aqueous formalin solution, 1.3 kg of water and 4.0kg of melamine are introduced into a 20 l stirred reactor and condensedat 80° C. with stirring in the course of 120 min.

[0108] In a second 200 l stirred reactor having a turbo stirrer, amixture of 6 kg of melamine, 6 kg of sodium montmorillonite (SüdchemieAG, Moosburg, Federal Republic of Germany) and 120 l of water is heatedto 80° C. and stirred for 2 hours, the sodium montmorillonite swelling.The pH of the suspension is adjusted to pH=5.0 with 1.15 kg of HCl andstirring is effected for 1 hour at 80° C. After cooling to roomtemperature, an aqueous solution of the aminoplast precondensate isadded to the stirred dispersion in the course of 30 min at high mixingintensity (40 m/s). After a reaction time of 60 min, the dispersion isdischarged and the modified inorganic particles are separated off in acellular filter, washed chloride-free and dried in vacuo at 75° C./8hours.

[0109] The yield of modified sodium montmorillonite is 17.1 kg.

[0110] The primary particles of modified sodium montmorillonite have amean particle diameter of 650 nm, determined by transmission electronmicroscopy.

[0111] ATR investigations of the modified inorganic particles indicateda surface coating of the particles with melamine resin.

[0112] For determining the content of free intercalated melamine in theintermediate silicate layers, 12 g of the modified inorganic particleshaving a layer structure were extracted for 48 hours with water. Afterconcentration of the extract and vacuum drying, 5.6 g of a white powderwere obtained. The dissolution in water and fractionation by means ofHPLC (Waters HPLC 2690, UV detection at 220 nm, Develosil RP aquaeuscolumn 5 mcm 250×2 mm, elution by 0.05 M NaH₂PO₄/acetonitrile (solventgradient) gave the following composition, based on the amount ofmelamine starting material: 69% by mass of melamine and 31% by mass ofhydroxymethylolmelamine and higher molecular weight oligomers.

EXAMPLE 5

[0113] A mixture of propylene copolymer (melt flow index 16.0 g/10 minat 230° C./2.16 kg, ethylene content 4.8% by mass) with 20% by mass ofammonium polyphosphate, 5% by mass of pentaerythritol, 0.15% by mass of2-tert-butyl-4,6-diisopropylphenol, 0.10% by mass ofbis-2,2,6,6-tetramethyl-4-piperidyl sebacate and 0.3% by mass, based ineach case on the propylene copolymer, of calcium stearate is metered at14.25 kg/h into a ZSK 27 Leistritz extruder, L/D=44, with side streammetering for pulverulent media and a decompression zone for vacuumdevolatilization, temperature profile20/200/200/200/200/200/200/200/200/200° C., melted and homogenized.Thereafter, the modified sodium montmorillonite according to example 3is metered via a metering apparatus for pulverulent media at 0.75 kg/hinto the polyolefin melt in zone 4. After thorough homogenization, themixture is devolatilized in the decompression zone, discharged andgranulated.

[0114] Specimens produced therefrom have a notched impact strength of 10kJ/m² and a modulus of elasticity of 2 250 MPa. Testing of the flameretardants according to UL 94 (1.6 mm) indicates classification in classV-0.

EXAMPLE 6

[0115] A mixture of propylene homopolymer (melt flow index 8.0 g/10 minat 230° C./2.16 kg), 20% by mass of ammonium polyphosphate, 5% by massof pentaerythritol, 0.15% by mass of 2-tert-butyl-4,6-diisopropylphenol,0.10% by mass of bis-2,2,6,6-tetramethyl-4-piperidyl sebacate and 0.3%by mass, based in each case on the propylene homopolymer, of calciumstearate is metered at 6.8 kg/h into a ZSK 27 Leistritz extruder,L/D=44, with side stream metering for pulverulent media and adecompression zone for vacuum devolatilization, temperature profile20/215/215/215/215/215/215/215/215/215° C., melted and homogenized.Thereafter, modified inorganic particles according to example 4 aremetered via a metering apparatus for pulverulent media at 0.68 kg/h intothe polyolefin melt in zone 4. After thorough homogenization, themixture is let down in the decompression zone, devolatilized, dischargedand granulated.

[0116] Specimens produced therefrom have a notched impact strength of 8kJ/m² and a modulus of elasticity of 2 450 MPa. Testing of the flameretardants according to UL 94 (1.6 mm) indicates classification in classV-0.

EXAMPLE 7 Preparation of the Laminating Resin Solution

[0117] 35 kg of a 30% aqueous aldehdye solution comprising 9:1formaldehyde/furfural, 8 kg of melamine, 2 kg of aniline and 2.5 kg of2-(2-hydroxyethylamino)-4,6-diamino-1,3,5-triazine are introduced into a150 liter stirred reactor having a reflux condenser and high-speeddisperser, adjusted to pH 7.0 with sodium hydroxide solution andcondensed at 80° C. with stirring in the course of 35 min. After coolingto room temperature, 1.2 kg of modified inorganic particles according toexample 1 are added to the reaction mixture and stirring is effected for45 min at 45° C.

[0118] Processing of the aminoplast solution with dispersed modifiedinorganic particles to give laminates.

[0119] For the production of the laminates, a decor paper (basis weight80 g m²) and a kraft paper as core paper (basis weight 180 g/m²) areimpregnated at 25° C. with a laminating resin solution which contains0.2% of 1:1 citric acid/phthalic acid as a curing agent, 5% by mass ofmodified inorganic particles and in each case 1% by mass of wettingagent and release agent. After drying in a through-circulation oven at140° C. to an alignment of 7.2%, the decor paper contains 58% by mass offilled laminating resin and the kraft paper contains 46% by mass offilled laminating resin. Two layers of the impregnated decor paper arethen compressed with a layer of core paper in between in a laminatingpress with a pressure of 90 bar at 155° C. for 120 s.

[0120] In order to test the toughness, the subsequent deformability ofthe resulting laminate was investigated. When the laminate is bentaround a 2.5 mm metal spindle heated to 160° C., no cracking of thelaminate occurs.

1. A modified inorganic particle having a layer structure, characterizedin that the modified inorganic particle has a mean particle diameter offrom 5 nm to 20 000 nm and an outer coat of from 0.1 to 20% by mass,based on the anhydrous inorganic particle, of aminoplasts and aninterlamellar content of from 20 to 5 000% by mass, based on theanhydrous inorganic particle, of a mixture of from 50 to 98% by mass ofsubstantially polyfunctional C₁-C₃₀ amino compounds of the typeconsisting of melamine, melamine derivatives, urea, urea derivatives,guanidine, guanidine derivatives, cyanamide, dicyandiamide, sulfonamidesand/or aniline and the salts thereof and from 2 to 50% by mass of water.2. The modified inorganic particle as claimed in claim 1, characterizedin that the inorganic particle having a layer structure is a silicate,phosphate, arsenate, titanate, vanadate, niobate, molybdate and/ormanganate, preferably a sheet silicate of the type consisting ofmontmorillonite, bentonite, kaolinite, muscovite, hectorite,fluorohectorite, kanemite, revdite, grumantite, ilerite, saponite,beidelite, nontronite, stevensite, laponite, taneolite, vermiculite,halloysite, volkonskoite, magadite, rectorite, halloysite, kenyaite,sauconite or borofluorophlogophite, and/or a synthetic sheet silicate,the sheet silicate furthermore preferably being a sheet silicate havingexchange cations of the type consisting of alkali metal, alkaline earthmetal, aluminum, iron and/or manganese cations.
 3. The modifiedinorganic particle as claimed in claim 1 or 2, characterized in that theaminoplasts are melamine resins, urea resins, cyanamide resins,dicyandiamide resins, sulfonamide resins, guanamine resins and/oraniline resins.
 4. The modified inorganic particle as claimed in claim3, characterized in that the melamine resins are polycondensates ofmelamine or melamine derivatives and C₁-C₁₀-aldehydes with a molarmelamine or melamine derivative/C₁-C₁₀-aldehyde ratio of from 1:1 to 1:6and the partial etherification products thereof with C₁-C₁₀-alcohols,the melamine derivatives preferably being melamines,diaminomethyltriazines and/or diaminophenyltriazines substituted byhydroxy-C₁-C₁₀-alkyl groups, hydroxy-C₁-C₄-alkyl(oxa-C₂-C₄-alkyl)₁₋₅groups and/or by amino-C₁-C₂-alkyl groups, particularly preferably2-(2-hydroxyethylamino)-4,6-diamino-1,3,5-triazine,2-(5-hydroxy-3-oxapentylamino)-4,6-diamino-1,3,5-triazine and/or2,4,6-tris(6-aminohexylamino)-1,3,5-triazine, ammeline, ammelide, melem,melon, melam, benzoguanamine, acetoguanamine,tetramethoxy-methylbenzoguanamine, caprinoguanamine and/orbutyroguanamine, and the C₁-C₁₀-aldehydes are preferably formaldehyde,acetaldehyde, trimethylolacetaldehyde, acrolein, furfurol, glyoxaland/or glutaraldehyde, particularly preferably formaldehyde.
 5. Themodified inorganic particle as claimed in claim 1, characterized in thatthe melamine derivatives are melamines, diaminomethyltriazines and/ordiaminophenyltriazines substituted by hydroxy-C₁-C₁₀-alkyl groups,hydroxy-C₁-C₄-alkyl(oxa-C₂-C₄-alkyl)₁₋₅ groups and/or byamino-C₁-C₁₂-alkyl groups, preferably2-(2-hydroxyethylamino)-4,6-diamino-1,3,5-triazine,2-(5-hydroxy-3-oxapentylamino)-4,6-diamino-1,3,5-triazine,2,4,6-tris(6-aminohexylamino)-1,3,5-triazine and/or2,4-(di-5-hydroxy-3-oxapentylamino)-6-methyl-1,3,5-triazine, ammeline,ammelide, melem, melon and/or melam.
 6. The modified inorganic particleas claimed in claim 1, characterized in that the urea derivatives arethiourea, and urea or thiourea substituted by C₁-C₁₀-alkyl groups,C₆-C₁₄-aryl groups, hydroxy-C₁-C₁₀-alkyl groups,hydroxy-C₁-C₄-alkyl(oxa-C₂-C₄-alkyl)₁₋₅ groups and/or byamino-C₁-C₁₂-alkyl groups.
 7. The modified inorganic particle as claimedin claims 1, 5 and 6, characterized in that the salts of melamine,melamine derivatives, urea, urea derivatives, guanidine, guanidinederivatives, cyanamide, dicyandiamide, sulfonamides and/or aniline aresalts with inorganic and/or organic anions, preferably fluorides,chlorides, bromides, iodides, sulfates, phosphates, borates, silicates,cyanurates, tosylates, formates, acetates, propionates, butyrates and/ormaleates.
 8. The modified inorganic particle as claimed in claim 4,characterized in that the C₁-C₁₀-aldehydes are formaldehyde,acetaldehyde, trimethylolacetaldehyde, acrolein, benzaldehyde, furfurol,glyoxal, glutaraldehyde, phthalaldehyde and/or terephthalaldehyde,preferably formaldehyde.
 9. A process for the preparation of modifiedinorganic particles having a layer structure, characterized in thatsuspensions of inorganic particles having a layer structure in water ormixtures of from 5 to 99% by weight of water and from 95 to 1% by massof C₁-C₈-alcohols, having a solids content of from 2 to 35% by mass, arehomogenized in a stirred reactor at from 20 to 100° C. and in aresidence time of from 10 to 180 min with solutions or suspensions ofpolyfunctional C₁-C₃₀ amino compounds of the type consisting ofmelamine, melamine derivatives, urea, urea derivatives, guanidine,guanidine derivatives, cyanamide, dicyandiamide, sulfonamides and/oraniline and the salts thereof in water or mixtures of from 5 to 99% byweight of water and from 95 to 1% by mass of C₁-C₈-alcohols, having asolids content of from 5 to 90% by mass, the amount by mass of thepolyfunctional C₁-C₃₀ amino compounds being from 20 to 5 000% by mass,based on the anhydrous inorganic particles, following the dispersion ofthe laden inorganic particles, optionally after the liquid phase hasbeen partially separated off, aminoplast prepolymers of the typeconsisting of melamine resins, urea resins, cyanamide resins,dicyandiamide resins, sulfonamide resins, guanamine resins and/oraniline resins having a number average molar mass of from 150 to 1 000,as a solution in water and/or in organic solvents or solvent mixtureshaving a resin content of from 30 to 98% by mass, and optionally from0.1 to 2.0% by mass, based on the aminoplast prepolymers, of acidiccatalysts are introduced at from 20 to 90° C. and are reacted, theaminoplast content of the dispersion being from 0.1 to 20% by mass,based on the anhydrous inorganic particles, the solids content of thedispersion with regard to inorganic particles being from 0.5 to 35% bymass and the residence time being from 10 to 45 min, and thereafter themodified inorganic particles are dried with removal of the liquid phaseat from 20 to 180° C. and in a residence time of from 0.1 to 8 hours.10. A process for the preparation of modified inorganic particles havinga layer structure, characterized in that suspensions of inorganicparticles having a layer structure in water or mixtures of from 5 to 99%by weight of water and from 95 to 1% by mass of C₁-C₈-alcohols, having asolids content of from 2 to 35% by mass, are homogenized in a stirredreactor at from 20 to 100° C. and in a residence time of from 10 to 180min with solutions or suspensions of polyfunctional C₁-C₃₀ aminocompounds of the type consisting of melamine, melamine derivatives,urea, urea derivatives, cyanamide, dicyandiamide, sulfonamidesguanidine, guanidine derivatives and/or aniline and the salts thereof inwater or mixtures of from 5 to 99% by weight of water and from 95 to 1%by mass of C₁-C₈-alcohols, having a solids content of from 5 to 90% bymass, the amount by mass of the polyfunctional C₁-C₃₀ amino compoundsbeing from 20 to 5 000% by mass, based on the anhydrous inorganicparticles, following the dispersion of the laden inorganic particles,optionally after the liquid phase has been partially separated off, from0.1 to 10% by mass, based on the anhydrous inorganic particles, ofC₁-C₁₀-aldehydes as from 5 to 50% solutions in water or mixtures of from5 to 99% by weight of water and from 95 to 1% by mass of C₁-C₈-alcohols,which optionally contain from 0.05 to 1% by mass, based onC₁-C₁₀-aldehydes, of acidic catalysts are added in the course of from 10to 90 min at from 50 to 90° C., and thereafter the modified inorganicparticles are dried with removal of the liquid phase at 20 to 180° C.and in a residence time of from 0.1 to 8 hours.
 11. The use of modifiedinorganic particles having a layer structure as claimed in claim 1 forflameproofing plastics, preferably in combination with inorganic and/ororganic salts having ammonium, alkylammonium, arylammonium, phosphonium,alkylphosphonium, arylphosphonium, alkali metal and/or alkaline earthmetal cations and/or phosphate, phosphite, phosphonate, silicate and/orborate anions, and/or with polyhydric alcohols of the type consisting oferythritol, pentaerythritol, pentitol and/or hexitol, and as additivesfor increasing the scratch resistance and UV stability and improving thebarrier properties of plastics and plastics laminates, and as a catalystor catalyst support.
 12. A polyolefin comprising from 1 to 60% by mass,based on the polyolefin used, of modified inorganic particles having alayer structure as claimed in claim 1 and optionally, as furtheradditives, inorganic or organic salts, fillers, reinforcing materials,polymeric dispersants, assistants and/or polyhydric alcohols, theinorganic or organic salts being salts having ammonium, alkylammonium,phosphonium, alkylphosphonium, arylphosphonium, alkali metal and/oralkaline earth metal cations and/or salts having phosphite, phosphate,phosphonate, silicate and/or borate anions, which may be contained in anamount of up to 25% by mass on the polyolefin, the fillers and/orreinforcing materials being inorganic or organic fillers and/or fiberswhich may be contained in an amount of up to 40% by mass in thepolyolefin, the polymeric dispersant being water-soluble,water-dispersible and/or water-emulsifiable polymers, which may bepresent in an amount of up to 3% by mass in the polyolefin, and thepolyhydric alcohols being polyhydric alcohols of the type consisting oferythritol, pentaerythritol, pentitol and/or hexitol, which may becontained in an amount of up to 15% by mass in the polyolefin.
 13. Athermosetting plastic comprising from 2 to 80% by mass, based on thethermosetting plastic used, of modified inorganic particles having alayer structure as claimed in claim 1 and optionally, as furtheradditives, inorganic or organic salts, fillers, reinforcing materials,polymeric dispersants, assistants and/or polyhydric alcohols, theinorganic or organic salts being salts having ammonium, alkylammonium,phosphonium, alkylphosphonium, arylphosphonium, alkali metal and/oralkaline earth metal cations and/or salts having phosphite, phosphate,phosphonate, silicate and/or borate anions, which may be contained in anamount of up to 60% by mass in the thermosetting plastic, the fillersand/or reinforcing materials being inorganic or organic fillers and/orfibers which may be contained in an amount of up to 70% by mass in thethermosetting plastic, the polymeric dispersants being water-soluble,water-dispersible and/or water-emulsifiable polymers which may becontained in an amount of up to 5% by mass in the thermosetting plasticand the polyhydric alcohols being polyhydric alcohols of the typeconsisting of erythritol, pentaerythritol, pentitol and/or hexitol,which may be contained in an amount of up to 30% by mass in thethermosetting plastic.
 14. A semifinished product or molding of apolyolefin or thermosetting plastic comprising modified inorganicparticles having a layer structure and optionally further additives asclaimed in claim 12 or 13 in the form of films, prepregs, fibers,sheets, pipes, coatings, hollow bodies, injection molded products andfoams.